Violet vat dyestuffs of the 2-thionaphthene-2-indolindigo series



-Patented one 29, 1926'.

,UNITED STATES PATENT OFFICE,

RICHARD AND WALTER BRIINNER, OF FRANKFORT-ON-THE-MAIN, GERMANY,

assmnons 'ro 'GRASSELLI nvns'rnrr conPoRArIoN, on NEW YORK, n. 1.,15.

CQBPOBATION OF DELAWARE.

VIOLET VAT ni'nsrurrs or run 2-'rHI oNarnrnnnn-amnopmmeo snares.

in Drawing. Application filed February 11, 1:126, Serial No. 87,676, and in Germany November 6, 1924,

Our invention relates to the production of the 2-th1onaph-. resulting from 7 new violet vat dyestuffs of thene-Q-indolindigo series,

the ,conden sation of 'oxythionaphthene-derivatives; corresponding probably to the general formula:- p

(wherein X means a halogen or an alkyl 715 group, Y means hydrogen, which may be substituted by a halogen 'or-an alkyl gro'up),

'with' an a-isatin-body of the general for-.

i 2 may contain further substituents, R means a halogen or an arylido group).

Espeftially valuable dyestuffs are obtained according .to this process if, in the COTldCIIS-H: tion as one component an oxythiona-phthem-derivative of the general formula:

Halogen Halogen (wherein Y means hydrogen which may be 40 substituted by a halogen or an alkyl group as the other componentuin a-isatm-body o the general formula:

(wherein'ltt means a halogen or an arylido oup) are used. i Dyestufis' ot a. similar character are group, i substituted by a halogen oran alkyl group corresponding chlorides (wherein X means a halogen or analkyl Y means hydrogen which may be and It means an aryl residue which may contain further substituents) are neweoinpounds and surpass 'the dyestuffs of the 2-thionaphthene-2-indolindigo series w are known hitherto by their exceptional brightness of shade and their excellent fastrespect to the best violet dyestuffs of the anthraquinone-series, their particular qualification for printing, because their fixation on the; fiber is, easy and their dyeingsrare easily discharged etofa. ure white.

The cotton and wool fabrics, dyed or printed with the present dyestnfis, also form a part of the (present invention.

The above .name oxythionaphthene-derivatives are new bodies.

fol lowing:

Starting from the corresponding substituted arylamins by transforming them into the (.Ol'l'GSPOlltllllQ' substituted arylthiogly- E collie acids and forming the ring either by with suitable acid contreating the latter (lensing agents, preferably with ehlorosultonic acid in the cold, or by converting the substituted arylthioglycollie acids into the by treating; them with phosphorus trichlori eor thionyl chloride) and treating the lltlikil' 'with suitable condensing agents, preferably with anhydrous aluminium chloride, phosphorus pentoxide and others-in the known manner.

Thusfor instance .7-dichl r and 5.7-

if the condensation of the above I (wherein :R means an aryl residue,whivh" to light lhey are fully equal m'thls but surpass these by A general well i working method of producing them is the at 150-153 C.

The alkylhalogeno-oxythionaphthenes may be obtained in an analogous manner, start- Y in from the corresponding halogenated to lthioglycollic acids.

9 ii. the 5-chloro-7-methloxythionaphthene ma be prepared by starting from the thioglyco lic acid of the formula:

v v v sonicoon, Y I

which is obtainable from 5-chloro-2toluidin. It forms in a pure state .feebly yellowish needles, meltin at 106-108 The isomeric 5-methyl- -chloro-oxythionaphthene is It forms when dry a dark violet powder, uble in cold concentrated sulfuric acid to a bluish black, in warm concentrated sulfuric acid to a bluish green, solution; \Vith alkaline hydrosulfit it yields an orange vat, and dyes in such a vat cotton and wool in bluish lyjolet shades. The dyeings thus produced are distinguished by their excellent 8 fastnesstowashing, light and chlorine.

If in this process instead of 5.7-dibromoisatinchloride the corresponding amount of 5.7-dichloroisatinchloride is used and it the 5.7-dichlorooxythionaphthene'is replaced by 90 the equivalent amount of 5.6.7-trichlorooxyformed in an analogous manner, starting from 3-chloro-4-toluidinof the formula:

it crystallizes froinwater or benzene as leaflets, melting at 120-12390. the 5.7 -dichloro- 6-methyl-oxythionaphthene may be repared for instance startinq from l-met xyl- 2.6-dichloro-3-aminobenzene, according to the same process; it crystallizes in yellowish leaflets, melting at 110 C.

The following examples illustrate the nature of our invention and in what manner i it is to be performed, the parts being by weight and all temperatures in centigrades.

Example 1. a

9,3parts of 5.7-dibromoisatin are suspended in about 50 parts of chloroben'zene.

Then 9 parts of phosphorus pentachloride,

are added and the mass is heated, until the formationof the'chloride is finished. To

this solution .a' solution of 6.6 parts of 5.7 dichlorooxythionaphthene in about the 'ten- I fold quantity of chlorobenzene is added and the mixture 1s heated for some hours to about -6070- C. When the condensation is finished and the'mass is cooled down, the separated ,dyestull is filtered oil and washed with chlorobenzene, at last with alcohol.

The reactions which take place'in the formation of the dyestufi are probably as follows:

- thionaphthene' a is obt ined, dyeing in bluish violet shades which aredistim guished by their unusual bri htness and by their excellent-fastness to lig t.

Identical dyestuffs are formed by using instead of the derivatives of a-isatin-chloride the corresponding derivatives of 'a-.isa-

tin arylides'. V p

' v Example 2. h 276 parts of 5.6.7-trichlorooxythionapb thene and 222 parts of a-isatinamlid are introduced in about 2000 parts of xylene or chlorobenzene or in a similarly acting solvent- 20 lid.

or diluent and the mixture is then heated'for stuff which separates'when cold .is filtered: some hours while stirring, until the formaoff anddried. It is probably forniedm ac tion of the dyestufl is finished. The dyecordance with the following reaction:

382 parts of this dyestufi are dissolved 5 an'orange-yellow vat, and dyes-cotton and in ahout5000 parts of concentrated sulfuric Wo ol m such a vat in full reddish violet acid at about C. and 320 parts ofbro shades." The dyeings are fast to washing, 10 mine are added. After some hours'the temlight and chlorine. v perature is increasedflto about 80 C. and 'Dyestufi's with similar'dyeing properties heating iscontinuedat this temperature, unare obtained by condensing in an analogous til the reaction is finished. 'Then' themass manner 5-methyl-7-chloro-oxythionaphthene is poured on ice, the precipitate is-filtered-ofl or -5,7-dichloro 6-methyl-oxythionaphthene 15 and washed. A Y with 5.7-dibro1noor -5-.7-dichloro-a-isatin- The product, thus obtained, dyes-cottonfchloridd; v and wool in similar shades as the dyestufl Identical dyestuffs are formed, it instead formed by condensing 5.6.7-trichl'orooxyof the mentioned 'a-isatin' chloride derivathionaphthene with 5.7-dibromoia-isatinani-f tives' the corresponding a-isatin 'arylide-derivatives are used. U I

Having now particularly described, and ascertained the'natu're of our said invention and in what manner the same is to be per- E mampZe U 10 parts of 5.7dibromoisatin are sus- Pended in about 50 Parts 9f chlorobenzenei we deal-fifth W we m' 25 a 1. As new com ounds violet vat d e tufi'. then 9 parts of phosphorus pentachlonde P Y s s are added and the mixture is heated, until of the g't'hlonaphthene'fz'mdohndlg) 561195 the formation of the 5.7-dibromo-a-1satin corresponding P l to the general chloride is finished. A solution of 7.5 parts mum:

I 0 of 5-chlor0-7-methyl-oxythionaphthene in o co 3 about the tenfold quantity of chlorobe zene X 4 is'added and the mixture isheated o the 5 B water-bath for some hours. The dyestufi', o i 2 v 2 thus formed, separates in a'crystalline state, Y 7 S .50 der, it dissolves in sulphuric acid monohycellent fastness especial 35 it is filtered off, washed and dried. It probably hasthe formula: v Y

wherein X means a halogen or an-alkyl' Br I group, Y means hydtogen, which may, be

substituted by a halogen-or an alkyl group 35 and R means an aryl residue, which may" contain further substituents, which are when dry violet powders, soluble in cold .concen i trated sulfuric acid to a greenish to bluish, In order to obtain it in a state easy to be in warm concentrated sulfuric acid to a 5 vatted it is dissolved in concentrated sulbluish 'gre'en solution, whch are separated furic acid and the solution, thus obtained, is therefrom by water in violetflakes, yielding poured on ice, filtered again and washed with alkaline hydrosuliiti. yellow to orange until th pl p t is u vat, from which cotton and wool is dyed in- The dyestutf is, when dry, a violet powfull violet to bluish violet shades of an ex- 95.

ly to light, which drate with a dark bluish reen color and dyestufis' are substantially identical with; forms with an alkaline by rosulht solution .yes'tufls obtainable from oxythionaphthn'ie derivatives, corresponding probably to the general'formula: a

' CH; /(2 Y r s (1) 1 v wherein X means a halogen or an alkyl group, Y means hydrogen, which may be substituted by a halogen "or an alkyl group, by condensing them with an a-isatin body of the general formula:

(a) El -C R wherein R means an arylresi-due, whichmay contain further substitutents, R means a halogen ora'n arylido roup.

2. As new compoun s violet vat dyestuffs of the 2-thionaphthene-2-indolindigo series oorrespondingprobably to the general formula: I v

oof 15cc 4 wherein X means a2 halogen or an alkyl group, Ymeans hydrogen, which may be sub.-.

stituted by a halogen or an alkyl group and R means a halogenated arylresidue, which are when dry violet powders, soluble in cold concentrated sulfuric acid to a greenish to bluish, in warm concentrated sulfuric acid to a bluish green solution, which are separated I therefrom by water in violet flakes, yielding with alkaline hydrosulfit a yellow to orange vat, from 'whiclrcotton and wool is dyed-1n Q .full violet to bluish violet shadesofan excellent fastness especially to light, which dyestuffs are substantially identical with dyestuffs obtainable from oxythionaphthene derivatives, corresponding probably to the general formula which are when dry' violet powders, solub V inoold concentrated sulfuric acid to a greengroup, ,Y means hydrogen, which may be substituted by a halogen or an alkyl grou by condensing them with an a-isatm bo y of the general formula:

Il -C wherein R means a. halo enated arylresidue, R a halogen or an aryliio group.

3. As new compounds violet vat dyestuffs of the 2- thionaphtheriefi-indolindigo series corpesponding probably to the general formu 9.:

wherein X nieans, a halogen or an alkyl group, Y-means hydrogen, which may be' substituted by a halogen or an alkyl group,

00 Halogen o==o I v n; V, (I) alonn ish-gto bluish, in warm concentrated sulfuric acid to a bluish green-solution, which are separated therefrom by water inviolet flakes, yielding with alkaline hydrosulfit a yellow to orange vat, from which cotton and wool is -dyed in full -violet to bluish violet shadesof an excellent fastness especially to li ht, which dyestuffs are substantially i entical with dyestuffs obtainable from from oxythionaphthene-derivatives, corre-' sponding probably to the general formula:

wherein X means a halogen or an alkyl group, Y means hydrogen, which may be substituted by a halogen or an alkyl group,

by condensing them with an a-isatin-body of the general formula:

'. of the 2-thionap thene-Q-indolindigo series formula:

wherein Y"mean 'si hydrogen, which may be substituted by a halogen or an alkyl group,

which are when dry-violet pwders,"s0luble '1 in cold concentrated sulfuric ,acid to a black-green, in warm concentrated sulfuric acid to a bluish-green solution, which are.

separated therefrom by water in violet flakes, yielding with alkaline hydrosulfit a golden yellow to yellowish orange vat from which cotton and wool is dyed in reddish violet to blue violet shades of an excellent fastness especially to light, .which dyestuffs i are substantially identical. with dyestuffs obtainable from .oxythionaphthene-deriva tives, corresponding probably to the general formula; V r

wherein means hydrogen, which maybe substituted-by a halogen oran'alkyl group,

general formula:

by condensing them with an a-isati n body of t e alogen wherein, R meansa halogen or an arylido tures.

which is when dry a violet powder, soluble in cold concentrated sulfuric acid to a bluish black, in warm concentrated sulfuric acid to a bluish green solution, which is separated therefrom in violet flakes, yielding with alkaline hydrosulfit an orange vat, from which cotton and wool is dyed in brilliant bluish violet shades of an excellent fastness, especially to light, which dyestufi' is substan tially identical with thedyestufi obtainable from y condensing it with an a-isatin body of the formula wherein'R means a halogen or an arylido group.

6. Textile material dyed with the dyestuffs as claimed in claim 1..

-7. Textile material dyed stuffs as claimed in claim 2. 8. Textile material dye-d stuffs as claimed in claim 3.

9. Textile material dyed with the dyewith the dyewith the dyestufi's as claimed in claim t.

10(Textile material dyed with the dyestuff as claimed in claim 5.

Intestimony whereof we aflix our signa- RICHARD HERZ. J a WALTER BRUNNER.

4. As new com uxids violet vat dyestufis' correspond ng probably to the general 

